Patent GB-918399-A (GB)
Title: Water dispersible carotenoid preparations and a process for their manufacture
IPC: A23L5/40
Filed: 1961-10-10
Abstract: A water-dispersible carotenoid preparation for foods and animal feeds comprises a carotenoid colouring agent and a salt of a higher fatty acid ester of ascorbic acid.  Carotenoid colouring agents mentioned are: carotene, including beta-carotone, lycopene, bixin, zeaxanthin, cryptoxanthin, lutein, canthaxanthin, b -apo- 81 -carotenal, b -apo-121-carotenal, b -apo-81-carotenoic acid and esters, particularly the methyl and ethyl esters, of hydroxyl and carboxyl-containing members of this group.  Salts of a higher fatty acid ester of ascorbic acid: preferably alkali-metal (sodium) or amino acid salts of the esters of myristic, palmitic ands tearic acids, particularly sodium or ammonium ascorbyl palmitate, lysine palmitoyl ascorbate and arginine palmitoyl ascorbate.  The preparation may include also a protective colloid such as gelatin, partially degraded gelatin, dextrin, gum arabic, tragacanth, a saccharose ester of a higher fatty acid such as saccharose oleate, ethylenediamine tetra acetic acid, or mixtures of these, to avoid the formation and precipitation of difficulty soluble calcium salts of the esters when the preparation is added to mineral or hard waters with a considerable content of calcium: an antioxidant such as ascorbic acid, tocopherol or nordihydroguaiaretic acid; and solution enhancing materials such as sodium tocopherol phosphate, sodium taurocholate and salts of p-amino-benzoic acid.  The preparation is prepared by forming a solution of a carotenoid in a volatile organic carotenoid diluent, preferably a poly-halogenated methane such as chloroform, carbon tetrachloride and methylene chloride, or benzene and carbon disulphide, in the presence of a salt of a higher fatty acid ester of ascorbic acid or of a mixture of a higher fatty acid ester of ascorbic acid with a basic agent, then removing the volatile diluent from the resulting mixture and, in the case where a dispersion in water is required and where removal of the volatile diluent has been effected by concentration to dryness, dispersing in water the residue from the concentration; the removal of the volatile diluent may be effected by concentration of the mixture in the presence of water.  The tendency of the carotenoids to crystallise during evaporation of the solution can be further hindered by adding lecithin and also small quantities of water, glycerine, fatty acids and their esters (especially glycerides). Basic agents mentioned are alkalimetal (sodium) carbonates and hydroxides, and amino acids such as ariginine and lysine. Sufficient colouring-agent is used to ensure an amount of 1% to 5% in the finished preparation.  The water-dispersible carotenoid preparation may be added to the following foods: fruit juices, mineral waters, syrups, confections, sugar, dextrin, glycerin, preserved foods, cheeses, dry beverage bases such as lemonade powder, tomato powder concentrates, powdered eggs, soup powder and pudding powders.  Many examples of the carotenoid preparations are disclosed, in some of which mixtures of carotenoid colouring agents are included.  In one example (6) 16,5g of cis beta-carotene, 16,5g of ascorbyl palmitate and 1,1g of alpha-tocopherol were dissolved in 375g of chloroform with warming; this solution was emulsified with a solution of 64,5g gelatin, 170g of water and 1,65g of sodium hydroxide, and the emulsion was dried in a drying roller under vacuum at 60 DEG C 100 mg of this betacarotene preparation was dispersed in 2ml of water with warming at 35 DEG C. The solution was heated to 60 DEG C and diluted with 8 ml. of water. The resulting coloured solution was mixed p  thoroughly with 150g of simple syrup and 10g of orange concentrate (1 : 6); after the addition of 2g of citric acid dissolved in 2 ml of water, the resulting solution was made up to one litre with water saturated with carbon-dioxide to give an orange drink having a beautiful yellow-orange colour.  According to another example (17), 44,5g of rennet casein was dissolved with stirring in 200g of distilled water mixed with 50 ml of ammonia solution and was maintained for 2 hours under a stirring at 60 DEG C; then 0,3g of sodium taurocholate was added (Solution I): 2,2g of cis beta-carotene, 1,9g of trans beta-carotene, 0,4g of ammonium ascorbyl palmitate 0,4g of ascorbyl palmitate and 0,4g of alpha-tocopherol were taken up in 30g of chloroform and heated to the boiling point of the chloroform (Solution II).  Solutions I and II were homogenised together, the organic solvents were removed from the emulsion by heating under a vacuum and the excess ammonia was liberated by drying in a vacuum drying oven at 40 DEG C or an oven with air circulation at 35 DEG C.ALSO:A water-dispersible carotenoid preparation for foods and animal feeds comprises a carotenoid colouring agent and a salt of a higher fatty acid ester of ascorbic acid.  Carotneoid colouring agents mentioned are: carotene, including beta-carotone, lycopene, bixin, zeaxanthin, cryptoxanthin, lutein, canthaxanthin, b -apo-81 - carotenal, b  - apo - 121 - carotenal, b  - apo-81-carotenoic acid and esters, particularly the methyl and ethyl esters, of hydroxyl and carboxyl-containing members of this group.  Salts of a higher fatty acid ester of ascorbic acid: preferably alkali-metal (sodium) or amino acid salts of the esters of myristic, palmitic and stearic acids, particularly sodium or ammonium ascorbyl palmitate, lysine palmitoyl ascorbate and arginine palmitoyl ascorbate.  The preparation may include also a protective colloid such as gelatin, partially degraded gelatin, dextrin, gum arabic, tragacanth, a saccharose ester of a higher fatty acid such as saccharose oleate, ethylene-diamine tetra acetic acid, or mixtures of these, to avoid the formation and precipitation of difficultly soluble calcium salts of the esters when the preparation is added to mineral or hard waters with a considerable content of calcium; an antioxidant such as ascorbic acid, tocopherol or nor-dihydroguaiaretic acid; and solution enhancing materials such as sodium tocopherol phosphate, sodium taurocholate and salts of p-aminobenzoic acid.  The preparation is prepared by forming a solution of a carotenoid in a volatile organic carotenoid diluent, preferably a polyhalogenated methane such as chloroform, carbon tetrachloride and methylene chloride, or benzene and carbon disulphide, in the presence of a salt of a higher fatty acid ester of ascorbic acid or of a mixture of a higher fatty acid ester of ascorbic acid with a basic agent, then removing the volatile diluent from the resulting mixture and, in the case where a dispersion in water is required and where removal of the volatile diluent has been effected by concentration to dryness, dispersing in water the residue from the concentration; the removal of the volatile diluent may be effected by concentration of the mixture in the presence of water.  The tendency of the carotenoids to crystallize during evaporation of the solution can be further hindered by adding lecithin and also small quantities of water, glycerine, fatty acids and their esters (especially glycerides).  Basic agents mentioned are alkali-metal (sodium) carbonates and hydroxides, and amino acids such as arginine and lysine.  Sufficient colouring-agent is used to ensure an amount of 1% to 5% in the finished preparation.  The water-dispersible carotenoid preparation may be added to the following foods: fruit juices, mineral waters, syrups, confections, sugar, dextrin, glycerin, preserved foods, cheese, dry beverage bases such as lemonade powder, tomato powder concentrates, powdered eggs, soup powder and pudding powders.  Many examples of the carotenoid preparations are disclosed, in some of which mixtures of carotenoid colouring agents are included.  In one example (6) 16.5 g. of cis beta-carotene, 16.5 g. of ascorbyl palmitate and 1.1 g. of alpha-tocopherol were dissolved in 375 g. of chloroform with warming; this solution was emulsified with a solution of 64.5 g. gelatin, 170 g. of water and 1.65 g. of sodium hydroxide, and the emulsion was dried in a drying roller under vacuum at 60 DEG  C. 100 mg. of this beta-carotene preparation was dispersed in 2 ml. of water with warming at 35 DEG  C.  The solution was heated to 60 DEG  C. and diluted with 8 ml. of water.  The resulting coloured solution was mixed thoroughly with 150 g. of simple syrup and 10 g. of orange concentrate (1 : 6); after the addition of 2 g. of citric acid dissolved in 2 ml. of water, the resulting solution was made up to one litre with water saturated with carbon-dioxide to give an orange drink having a beautiful yellow-orange colour. According to another example (17), 44.5 g. of rennet casein was dissolved with stirring in 200 g. of distilled water mixed with 50 ml. of ammonia solution and was maintained for 2 hours under stirring at 60 DEG  C.; then 0.3 g. of sodium taurocholate was added (Solution I): 2.2 g. of cis beta-carotene, 1.9 g. of trans beta-carotene, 0.4 g. of ammonium ascorbyl palmitate, 0.4 g. of ascorbyl palmitate and 0.4 g. of alpha-tocopherol were taken up in 30 g. of chloroform and heated to the boiling point of the chloroform (Solution II).  Solutions I and II were homogenized together, the organic solvents were removed from the emulsion by heating under a vacuum and the excess ammonia was liberated by drying in a vacuum drying oven at 40 DEG  C. or an oven with air circulation at 35 DEG  C.